Process for the treatment of textiles and the textiles obtained



United States Patent 3,239,303 PROCESS FUR THE TREATMENT 01F TEXTILES AND THE TEXTHLES UBTAIINED Leo S. Luslsin, Philadelphia, and Stella W. King, Elkins Park, Pam, assignors to Rohm d; Haas Company, Philadelphia, Pin, a corporation of Delaware No Drawing. @riginal apptication Oct. 19, 1959, Ser. No. 847,103, now Patent No. 3,074,898, dated .Tan. 22, 1963. Divided and this application .l'nne 6, 1962, Ser. No. 200,308

Claims. (Cl. 8-1163) This application is a division of application Serial No. 847,103, filed October 19, 1959, now US. Patent 3,074,898, which in turn is a continuation-in-part of application Serial No. 792,991, filed February 13, 1959, now abandoned.

This invention relates to compositions for the treatment of textile materials, and it is particularly concerned with the treatment of textile materials of wool and cellulosic type to improve their characteristics, especially to render the fabrics resistant to crushing and to shrinkage on laundering. It is also concerned with the treated fabrics thereby obtained and with methods for treating fabrics with the novel compositions.

Heretofore, condensates of formaldehyde with melamine, urea and their derivatives including cyclic urea derivatives, such as N,N-ethyleneurea and methylol melamines and ureas and their alkylated derivatives and also N,N-trimethyleneurea, have been applied to wool and cellulosic fabrics, such as cotton, for the purpose of imparting crush-resistance and reduced shrinkage on laundering. However, fabrics treated with these condensates pick up chlorine during bleaching operations using chlorine, such as those using it in the form of a hypochlorite. On ironing the fabrics that have been bleached in this manner, severe discoloration and/ or loss in tensile and/ or tear strengths have generally resulted. In those cases where severe discoloration is encountered, the treatment with these condensates is unsuitable, especially when a white fabric is desired. In some cases, as much as 90% loss in strength is encountered as a result of the action of heat, as in ironing, on fabrics treated with these condensates and bleached with chlorine. The presence on a fabric of a thermoset condensate of formaldehyde with melamine frequently gives rise to some discoloration of the fabric on the mere treatment with a hypochlo-rite bleach unless care is taken to avoid excess chlorine and elevated temperatures. Ironing in such cases serves to aggravate the discoloration.

The Suen patent, No. 2,730,427, discloses the treatment of textile materials for imparting resistance to shrinkage and creasing with certain diglycidyl ethers having the Formula I:

wherein R is an alkylene group of from 2 to 6 carbon atoms. United States Patent 2,752,269 discloses the use of other types of glycidyl polymers and condensates such as those obtained by condensation of glycerol and epichlorohyd-rin and polymers of allyl glycidyl ether. The use of the glycidyl compounds of these patents, however, is quite expensive and comparatively inefficient with respect to certain nitrogen-containing condensates, and especially those of formaldehyde with N,N'-ethyleneurea and melamine. It is generally required that about three times as much of one of these .glycidyl compounds must be applied to a cotton fabric to obtain crush-proofing action comparable to that obtained with a given amount of the nitrogen-containing aminoplasts just mentioned. Generally, also the diethers are two or three times as expensive Patented Mar. 8, 1956 as these aminoplasts and as much as fifteen times the cost of the simpler urea-formaldehyde condensate.

U.S. Patent 2,794,754 discloses the use of a mixture of an aminoplast condensate with a compound containing a plurality of Vic-epoxy groups. The compounds of this patent, however, are comparatively inefiicient in protecting the fabric from chlorine damage by certain nitrogencontaining condensates, and especially those of formaldehyde with N,N'-ethyleneurea and melamine, when used in admixture therewith. In addition, the vic-ep0xy compounds tend to pick up iron in hard water and thereby produce a discoloration on washing of the fabric which cannot be removed by normal bleaching operations.

It has been found in accordance with the invention that the incorporation of a minor proportion of certain watersoiuble or easily water-dispersible oxetanes in aqueous solutions of water-soluble aminoplast condensates selected from the group consisting of condensates of formaldehyde with aminotriazines, certain triazones, N,N-trimethyleneurea, and N,N-ethyleneurea, and their alkylated derivatives serves to eliminate, or reduce to within practical limits, the chlorine damage that would otherwise occur as a result of the treatment with such aminoplasts. Surprisingly, the improvement is accomplished without the necessity to apply excessive quantities of the shrinkproofing or crease-proofing composition in spite of the fact that the oxetanes are incapable of crease-proofing cellulosic fabrics when applied without an aminoplast under conditions similar to those under which the mixture is appiied. The oxetanes of the present invention are from five to ten times as efficient as the vie-epoxy compounds of the US. Patent 2,794,754 in reducing chlorine damage by discoloration and degradation caused by the aminoplast condensates and have little or no tendency to pick up iron from hard waters as the vie-epoxy compounds do.

For convenience of reference hereinafter, the aminoplast is referred to as component A and constitutes the major or predominant part of the shrink-proofing, creaseproofing or crush-proofing components of the composition. The oxetane component is hereinafter referred to as component B and constitutes from about 5% to about 40% by weight of the effective components, that is the total weight of the aminoplast and oxetane components. For most purposes, from the standpoint of cost, efficiency, optimum freedom from discoloration, and minimum tensile loss on ironing or heating after chlorination, it is preferred to use from 5% to 20% by weight of component B and 95% to by weight, respectively, of component A.

In accordance with the presentinvention, the aminoplast compositions with which the invention is concerned are water-soluble in character and include the simple condensates of N,N'-ethyleneurea, certain triazones described hereinafter and aminotriazines, such as melamine or its derivatives including N-(C C )alkylmelamines, N,N-di(C C )alkylmelamines, and N,N'-di(C C )alkylmelamines, with formaldehyde as well as the alkylated methylol derivatives thereof, in which the alkylation is effected with lower alcohols from 1 to 3 carbons or with small proportions of higher alcohols, such as the butyl alcohols or with mixtures of such higher alcohols with the lower alcohols, so that in any event the alkylated methylol derivatives are water-soluble or self-dispersible readily in water. Any water-soluble condensate of formaldehyde with melamine, N,N-ethyleneurea, or N,N- trimethyleneurea may be employed. Examples of specific compounds that may be used include trimethylolmelamine, dimethylol-N,N'-ethyleneurea, and dimethylol- N,N'-trimethyleneurea. The triazones that may be used include the polymethylol tetrahydro-s-triazones substituted in the 5-position by an alkyl or hydroxyalkyl group. These triazones have the formula II:

N-CHzOH N I t (II) where R is selected from the group consisting of 2-hydroxyethyl, Z-hydroxypropyl, and alkyl groups having 1 to 4 carbon atoms. In addition, the alkylated derivatives of these polymethylol condensates obtained from the lower alcohols from methyl through butyl may be employed. Examples include dimethoxymethyl-l I,N-dimethylmelamine, dimethoxymethyl \LN ethyleneurea, dimethoxymethyl 5 (B hydroxymethyl)tetrahydro striazone-Z, and so on. Again, it should be noted that the condensates employed as component A may be fairly sharply defined compounds including those just named as well as others, or it may comprise mixtures of compounds of varying degrees of substitution wherein the number of methylol groups or alkoxymethyl groups may be different in the several compounds Within the mixture. For the most efficient action, the aminoplasts derived from N,N-ethyleneurea and from melamine are preferred.

Component B may consist of any oxetane within the scope of Formula III following:

R0 H,o-( :oH2 0c..H..), 0H

0-CH2 (III) in which R is selected from the group consisting of H, CH (C I-I OH, CH CI, and alkyl groups having 1 to 8 carbon atoms,

11 is an integer having a value of 2 to 3, and x is an integer having a value of 1 to 11, preferably 1 to 3.

The aqueous solution of the water-dispersible condensates, including component A and component B, may contain such condensates in a concentration in about 2% to 25% or more, based on total condensate solids. The particular concentration applied in any given instance may depend on the purpose for which the condensate mixture is applied and on the particular substrate or fabric to which it is applied. In the case of cotton, the concentration is preferably from 2% to 12%, Whereas in application to rayon the concentration is preferably 5% to 20%, when the purpose of the application is to impart creaseresistanee, crush-resistance, or shrinkage stabilization. In the case of wool, the concentration is preferably from 5% to 15%. While it is generally unnecessary, component A and component B may be reacted together provided any such reaction leaves the final condensate in a water-soluble condition. However, for most purposes, it is preferred not to co-react these components.

The solution containing the mixture of condensates (component A and component B) or the co-reacted condensates is stable when subjected to ordinary conditions of storage and can be sold, shipped and stored as such. Shortly before use, an acidic catalyst may be added, if desired, as pointed out hereinafter.

An acidic catalyst for catalyzing the condensation of the aminoplast and the reaction of the cellulose with the oxetane and the aminoplast is applied to the fabric either simultaneously with the condensates or before or after the mixture of condensates is applied. Preferably the acidic catalyst is dissolved in the aqueous solution of the mixture of condensates. Suitable catalysts include ammonium phosphate, ammonium fiuoborate, ammonium thiocyanate, hydrochloric or other acid salts of a hydroxy aliphatic amine including 2-methyl-2-amino-1-propanol, Z-methyl-Z-amino-1,3-propandiol, tris-(hydroxymethyl)aminomethane, 2-phenyl-2-amino-1-propanol, 2-

4- methyl-2-amino-l-pentanol, Z-aminobutanol, triethanolamine, 2-amino-2-ethyl-l-butanol, and also ammonium chloride, pyridine hydrochloride, aluminum chloride, benzyldimethylammonium oxalate, magnesium perchlorate, zine silicofiuoride, zinc perchlorate, magnesium thiocyanate, zine thiocyanate, zinc fiuoborate, zinc nitrate, boron fluoride, and especially the boron fluoride ether complex of the boron fluoride water complex, hydrogen fluoride, hydrochloric acid, ammonium chloride, ammonium acid fluoride, phosphoric acid, oxalic acid, tartaric acid, citric acid, sulfuric acid and sodium bisulfate. The preferred catalysts which seem to be outstanding in their efiiciency of action and freedom from detrimental effect on fabrics, especially with cellulosic types of fabrics, are the Zinc salts such as Zinc fiuoborate and zinc nitrate. The catalyst is generally introduced into the aqueous solution of the condensates at a concentration of about 0.1 to 2% and preferably approximately 1%. The catalyst may be present in an amount from about /2 to about 25% on the weight of condensaate solids (including the aminoplast and oxetane).

The compositions of the present invention may be applied to fibers, filaments, yarns, or fabrics of wool or cellulosic type and especially those of cotton or rayon for various purposes. For example, they may be applied simply to modify the feel or texture of the surface of the fabrics. When applied in greater quantities, the condensates of the present invention may be used to make the fabrics wrinkle-resistant, crush-resistant and crease-resistant. The application of increasing amounts of the condcnsates serves to provide proportionately increased reduction in shrinkage of the treated fabric on laundering, and when about 3% to 7% by weight of the condensate, based on the weight of the fabric, is applied, the wool or cellulosic fabric is generally substantially stabilized against shrinkage on laundering. The application of the condensates of the present invention may be employed for the purpose of aiding embossing operations. They also may be applied to fabrics as part of a process for their conversion to pliss fabrics and embossed fabrics.

The aqueous solution of the condensates may be applied by spraying, brushing, dipping, as in padding, or by rollercoating. After the application, excess may be removed, as by squeegeeing. The treated fabric is then dried, such as by air-dryin' at room temperature or by the treatment with heated air under conventional conditions. After the fabric has been dried, the condensate mixture is baked or cured on the fabric at a temperature of about 220 to 450 F. or higher, depending on the particular substrate. The time may be varied generally in inverse proportions to the temperature. For example, the time may vary from about five seconds to half an hour. A time of 30 seconds at 400 F. is quite practical and a time of 15 to 30 minutes at 220 F. is generally satisfactory. The baking operation may simply be a continuation of the drying operation so that drying and curing may be effected in essentially a one-stage procedure.

The drying and/or the baking may be effected by any suitable means for applying the heat, such as by the application of heated air currents, by infra-red radiation or by high frequency electric induction.

The oxetanes of Formula III are either known compounds or homologs of known compounds made in the same way as the latter but with homologous starting materials. Examples of preparation of the compounds are given in Serial No. 347,103, supra.

In the following examples, which are illustrative of the invention, the parts and percentages given are by weight unless otherwise noted. The chlorination test method referred to in the examples follows the A.A.T.C.C. (69- 1952) procedure in general except the temperature of chlorination and that of ironing indicated hereinafter. The actual procedure used involves the treatment with a hypochlorite solution containing 0.25% available chlorine at a temperature of F.:2 F. for 15 minutes with t is the tensile strength after chlorination only, and I is the tensile strength after both chlorination and ironing (or scorch test).

where Example 1 (a) An aqueous solution is prepared containing 2.5% of 3 methyl-3-hydroxymethyl-oxetane, 5% of dimethylol- N,N'-ethyleneurea, and 0.4% of zinc fiuoborate as a catalyst. A white cotton fabric is padded through this solution, dried at 240 F. for 5 minutes and then heated at 340 F. for 5 minutes to cure the resin.

(b) Another piece of the same cotton fabric is treated in the same way except that the oxetane was reduced to 0.5%.

Another piece of the same cotton fabric is treated in the same way except that the oxetane was reduced to zero.

After five full Sanforize washes, the fabrics are subjected to the chlorination test above. In all cases, yellowing after ironing is either non-existent or negligible.

The results of testing for crease-proofing and chlorine damage are shown in the following table (wherein the values given for crease-recovery, are the average of the values for warp and filling):

Table I Oease- Tensile Recovery Strength before Percent Discoloration on Example Angle, chlorination loss in Chlorination and degrees test (Warp), Tensile Ironing s. /sq. in.

114 42 10 None. 118 43 10 None. 120 42 86 Severe (Brown);

An aqueous solution is prepared containing 1.0% 3- methyl-3-hydroxymethyl-oxetane, of dimethylol-N,N- trimethyleneurea, and 0.5% of zinc fluoborate as a catalyst. A while cotton fabric is padded through this solution, dried at 240 F. for 5 minutes and then heated at 340 F. for 5 minutes to cure the resin.

After 5 full Sanforize washes the fabric is subjected to the chlorination test with negligible discoloration.

Similar results are obtained when the oxetane is replaced by 3 methyl 3-(hydroxyethoxyethoxymethyl)- oxetane (Example C of Serial No. 847,103).

EXAMPLE 3 (a) An aqueous solution is prepared containing 0.5% of 3-methyl-3-hydroxymethyl-oxetane, 5% of dimethylol trimethoxymethyl melamine, and 0.5 of zinc fluorborate as a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(11) Another piece of the same cotton fabric is treated in the same Way except the oxetane is omitted. After five full Sanforize was-hes and subjection to the chlorination test above, the results obtained are those listed in Table II.

T able II BEFORE CHLORINATION TEST Elmendorl Chlorine Damage Tear Tensile Orease- Strength Strength Example Recovery average (Warp), Discolora- Angle, (Warp and lbs/sq. Percent tion on degrees Fill) in in. Loss in Chlorinalbs. Tensile tion and Ironing 1.4 43 2 None. 1. 36 41 15 Yellow.

Similar results are obtained when the oxetane is replaced by 3-(t-butyl)-3-hydroxyethoxymethyl-oxetane.

EXAMPLE 4 (a) An aqueous solution is prepared containing 1% of 3-methyl-3-hydroxymethyl-oxetane, 6% of dimethylol-S- ethyl-tetrahydrotriazone-Z, and 1.0% of zinc nitrate as a catalyst. Application to white cotton fabric is made by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same way except the oxetane is omitted. After live full Sanforize washes and subjection to the chlorination test, the results are as listed in Table III.

Similar results are obtained when the oxetane is replaced by 3-(n-octyl) 3 hydroxy(ethoxy) methyl)- oxetane.

Table III CHLORINE DAMAGE Percent Loss Diseoloration Example in Tensile on Chlorintu Strength tion and Ironing 6 Slight. 15 Yellow.

(0) Similar results are obtained when the triazone is replaced with dimethylol-5-(fi-hydroxyethyl)-tetrahydros-triazone-Z.

Similar results are obtained when the oxetane is replaced by 3,3-dihydroxymethyl-oxetane.

It is to be understood that changes and variations may be made without departing from the spirit and scope of the invention as defined in the appended claims.

We claim:

11. An article of manufacture comprising a cellulose fabric modified by chemical reaction, at a temperature of at least about 220 F. for a period of at least about five seconds, with a mixture of 60 to 95% by weight of a Water-dispersible aminoplast condensate selected from the group consisting of condensates of formaldehyde with a compound selected from the group consisting of N,N- ethyleneurea, N,N'-trimethyleneurea, a tetrahydro-s-triazone-Z substituted in the 5-position with a group selected from the group consisting of fl-hydroxyethyl, ,B-hydroxypropyl, and (C C )-alkyl groups, and aminotriazines and 5 to 40% by weight of an oxetane of the formula 7 in which R is selected from the group consisting of H,

--CH OH CH Cl, and alkyl groups having 1 to 8 carbon atoms,

)1 is an integer having a value of 2 to 3, and

x is an integer having a value of 1 to 11,

in contact with /2 to 25% by Weight, based on the total Weight of aminoplast and oxetane, of an acidic catalyst.

2. An article of manufacture comprising a cellulose fabric modified by chemical reaction, at a temperature of at least about 220 F. for a period of at least about five seconds, with a mixture of 60 to 95 by weight of a water-soluble condensate of formaldehyde with N,N'- ethyleneurea, and 5 to 40% by weight of an oxetane as defined in claim 1, in contact with /2 to 25% by weight, based on the total Weight of aminoplast and oxetane, of an acidic catalyst.

3. An article of manufacture comprising a cellulosic fabric modified by chemical reaction, at a temperature of at least about 220 F. for a period of at least about five seconds, with a mixture of 60 to 95% by Weight of a water-soluble condensate of formaldehyde with melamine and. 5 to 40% by weight of an oxetane as defined in claim 1, in contact with /2 to 25% by weight, based on the total weight of aminoplast and oxetane of an acidic catalyst.

4. An article of manufacture comprising a cellulosic fabric modified by chemical reaction, at a temperature of at least about 220 F. for a period of at least about five seconds, with a mixture of 60 to 95% by Weight of a water-soluble condensate of formaldehyde with 5-ethyltetrahydro-s-triazone-2 and 5 to 40% by weight of an oxetane as defined in claim 1, in contact with /2 to 25 by weight, based on the total weight of aminoplast and oxetane, of an acidic catalyst.

5. A process for treating a fabric comprising applying to a cellulose fabric an aqueous dispersion containing at least 2% by weight of a mixture of (1) 60 to 95% by weight of a water-dispersible aminoplast condensate selected from the group consisting of condensates of formaldehyde with a compound selected from the group consisting of N,N'-ethyleneurea, N,N-trimethyleneurea, a tetrahydro-s-triazone-Z substituted in the 5-position with a group selected from the group consisting of fl-hydroxyethyl, fi-hydroxypropyl, and (C -QQ-alkyl groups, and aminotriazines and (2) 5 to 40% by Weight of an oxetane of the formula R is selected from the group consisting of H, CH OH, -CH Cl, and alkyl groups having 1 to 8 carbon atoms,

11 is an integer having a value of 2 to 3, and

x is an integer having a value of 1 to 11, preferably and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensate and the oxetane, and. drying and curing the mixture on the fabric at a temperature of at least about 220 F. for a period of at least about five seconds.

6. A process for treating a fabric comprising applying to a cellulose fabric an aqueous dispersion containing 8 about 2 to 25 by weight of a mixture of (1) to by weight of a water-dispersible aminoplast condensate selected from the group consisting of condensates of formaldehyde With a compound selected from the group consisting of N,N'-ethyleneurea, N,N'-trirnethyleneurea, a tetrahydro-s-triazone-Z substituted in the 5-position with a group selected from the group consisting of fi-hydroxyethyl, B-hydroxyprtopyl, and (C -C )-alkyl groups, and amino-triazines and (2) 5 to 40% by weight of an oxetane as defined in claim 5 and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensates and the oxetane, and drying and curing the mixture on the fabric at a temperature of 220 F. to 450 F. for a period of about 5 seconds to about half an hour.

7. A process for treating a fabri comprising applying to a cellulose fabric an aqueous dispersion containing about 2 to 25% by weight of a mixture of (l) 60 to 95% by weight of a water-soluble condensate of formaldehyde with melamine and (2) 5 to 40% by weight of an oxetane as defined in claim 5, and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensate and the oxetane, and drying and curing the mixture on the fabric at a temperature of at least about 220 F. for a period of at least about five seconds.

8. A process for treating a fabric comprising applying to a cellulose fabric an aqueous dispersion containing about 2 to 25% by weight of a mixture of (1) 60 to 95% by weight of a water-soluble condensate of formaldehyde with 5-ethyltetrahydro-s-triazone-2 and (2) 5 to 40% by weight of an oxetane as defined in claim 5, and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensate and the oxetane, and drying and curing the mixture on the fabric at a temperature of at least about 220 F. for a period of at least about five seconds.

9. A process for treating a fabric comprising applying to a cellulose fabric an aqueous dispersion containing about 2 to 25% by weight of a mixture of (1) 60 to 95% by Weight of a water-soluble condensate of formaldehyde with N,N-ethyleneurea and (2) 5 to 40% by weight of an oxetane as defined. in claim 5, and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensate and the oxetane, and drying and curing the mixture on the fabric at a temperatu're of at least about 220 F. for a period of at least about five seconds.

10. A process for treating a fabric comprising applying to a cellulose fabric an aqueous dispersion containing about 2 to 25% by weight of a mixture of (1) 60 to 95% by weight of a Water-soluble condensate of formaldehyde with S-(B-hydroxyethyl)-tetrahydro-s-triazone-2 and (2) 5 to 40% by weight of an oxetane as defined in claim 5, and about 0.1 to 2% of an acidic catalyst for catalyzing the reaction of the cellulose fabric with the condensate and the oxetane, and drying and curing the mixture on the fabric at a temperature of at least about 220 F. for a period of at least about five seconds. 

5. A PROCESS FOR TREATING A FABRIC COMPRISING APPLYING TO A CELLULOSE FABRIC AN AQUEOUS DISPERSION CONTAINING AT LEAST 2% BY WEIGHT OF A MIXTURE OF (1) 60 TO 95% BY WEIGHT OF A WATER-DISPERSIBLE AMINOPLAST CONDENSATE SELECTED FROM THE GROUP CONSISTING OF CONDENSATES OF FORMALDEHYDE WITH A COMPOUND SELECTED FROM THE GROUP CONSISTING OF N,N''-ETHYLENEUREA, N,N''-TRIMETHYLENEUREA, A TETRAHYDRO-S-TRIAZONE-2 SUBSTITUED IN THE 5-POSITION WITH A GROUP SELECTED FROM THE GROUP CONSISTING OF B-HYDROXYETHYL, B-HYDROXYPROPYL, AND (C1-C4)-ALKYL GROUPS, AND AMINOTRIAZINES AND (2) 5 TO 40% BY WEIGHT OF AN OXETANE OF THE FORMULA 